CN102408942B - Device and preparation method for hydrorefining basic oil from waste internal-combustion engine oil - Google Patents
Device and preparation method for hydrorefining basic oil from waste internal-combustion engine oil Download PDFInfo
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Abstract
The invention relates to a device and a preparation method for hydrorefining basic oil from waste internal-combustion engine oil, and belongs to the technical field of a waste internal-combustion engine oil regeneration process. The device comprises a sedimentation and filtration system, a pretreatment system, a film distiller, a molecular distiller, a hydrogenation reactor, a stripping tower and a rectifying tower, wherein the sedimentation and filtration system, the pretreatment system, the film distiller, the hydrogenation reactor, the molecular distiller, the hydrogenation reactor, the stripping tower and the rectifying tower are successively communicated; the sedimentation and filtration system is used for filtering free water and mechanical impurities in the waste sedimentation and filtration system; the pretreatment system is used for removing water, petroleum acid, colloid bitumen and low hydrocarbon components; the film distiller is used for removing light components with a boiling point of less than 350 DEG C; the molecular distiller is used for separating out fractions with a boiling point of more than 350 DEG C and heavy components in the waste internal-combustion engine oil; the stripping tower is used for mixing gas with liquid and further separating in a hydrogenating process; and the rectifying tower is used for fractioning lubricating oil basic oil with different viscosities. The device has reasonable structure design; the preparation method has environmentally-friendly process flow and no pollution; and by using the device and the preparation method, the waste internal-combustion engine oil can be refined into high-purity basic oil.
Description
Technical field
The present invention relates to a kind of device and preparation method of waste internal-combustion engine oil refining base oil, belong to the technology for regenerating waste internal combustion engine oil technical field.
Background technology
At present, lubricating oil is widely used in the industries such as Automobile Transportation, manufacture, mechanical workout, chemical industry, food, fast development and growth along with industry and national economy, its demand and consumption are also increasing day by day, the internal lube oil annual turnover is over 1,000 ten thousand tons at present, and every year be 10% above speed increase, this also means the annual waste internal-combustion engine oil that at least produces 6,000,000 tons, along with automobile industry development also has, continues the trend increased.Discarded lubricating oil is mainly because life-time service is infiltrated impurity and additive metamorphic, be exactly waste internal-combustion engine oil small part oxicracking in addition and cause viscosity to change and form asphalt colloid, the base oil component of the overwhelming majority does not change, as long as separate processing by certain technique means, still can obtain standard compliant base oil.
Along with the exhaustion day by day of petroleum resources and the enhancing of mankind's environmental consciousness, waste internal-combustion engine oil recovery, purification and recycle also have been subject to the great attention of countries in the world, at the waste and old recovery of oil of China, purification, cyclic utilization rate less than 5%, most of sour soil method and Pyrolysis gas oil PGO technique of adopting, its Technology is backward, the rate of recovery is low, poor product quality, can cause secondary pollution.
Regulation according to national Hazardous Waste List, waste mineral oil (HW08) refers to used oil, waste diesel, Waste gasoline, waste crude oil, useless vacuum pump oil, waste hydraulic oil, useless heat-treated oil, useless camphor wet goods be take each class lubricating oil that mineral oil is basis and is lost the oils that original function is scrapped, toxophoric property material, rank the 8th in national Hazardous Waste List, the sulfide that it includes, additive, petroleum-type polynuclear aromatics (benzopyrene) is the carcinogenic and mutagenic compounds of generally acknowledging, nutrient rich, pollution especially severe to water and soil, if the mankind quote contaminated water quality for a long time, the chronic poisoning symptom will appear.
The technology for regenerating waste internal combustion engine oil technical development: distillation-pickling-clay-filtered route and pickling-distillation of band soil is made with extra care is main reclaiming process, adopt distillation-carclazyte technique, the refining sulfuric acid carclazyte that still adopts, this oil quality is poor, easily oxidation, contain a large amount of benzopyrenes materials in acid sludge, serious environment pollution.
Summary of the invention
The object of the invention is to solve the weak point that above-mentioned prior art exists, a kind of reasonable in design is provided, technical process is environment friendly and pollution-free, the waste internal-combustion engine olein can be made to device and the preparation method of high purity base oil.
A kind of device of hydrorefining basic oil from waste internal-combustion engine oil, its special character be to comprise be connected successively for filtering the sedimentation filtering system 1 of waste internal-combustion engine oil free-water and mechanical impurity, for removing, anhydrate, petroleum acid, the pretreatment system 2 of colloidal bitumen and low hydrocarbon component, for removing the film distillator 3 of 350 ° of following light component of C of boiling point, for separating of going out the 350 ° of above cuts of C of boiling point in waste internal-combustion engine oil and removing the molecular still of heavy component in waste internal-combustion engine oil, hydrogenator, mix the stripping tower 4 further separated for the hydrogenation process vapour-liquid, rectifying tower 5 for fractionation hydrofined oil different motion viscosity lubricant base.
Described molecular still comprises first step molecular still 6, the second stage molecular still 7 of series connection;
Described molecular still is short-distance distiller, comprise cylindrical shell 11 and be installed on the motor rotating mechanism 12 of cylindrical shell 11 tops, the agitator 14 that motor rotating mechanism 12 first distributor 15 interior with being located at cylindrical shell 11 reaches with the first scraper plate 17 is connected, the inside of agitator 14 is provided with condenser, condenser is connected with the first collector 16, cylindrical shell 11 outer cover are provided with in the first chuck 13, the first chucks 13 and are filled with heat-conducting medium; During work, by the 12 rotating centrifugal motions of motor rotating mechanism, the first distributor 15 is thrown to waste internal-combustion engine oil on the inner heating surface of chuck, and the first scraper plate 17 knifing, reach the liquid level effect of constantly updating, be convenient to the evaporation of material component thermally equivalent, pass into mobile coolant media in stainless steel shell-and tube condenser in agitator 14, for the oil vapour condensation rapidly evaporation, become liquid and collect, heavy component is not evaporated, and by molecular still bottom the first collector 16, is collected;
Described hydrogenator comprises the first hydrogenator 8, the second hydrogenator 9, the 3rd hydrogenator 10 be in series;
The device of hydrorefining basic oil from waste internal-combustion engine oil of the present invention also comprises that heating system 31, circulating water system 32, water-circulation type vacuum and high vacuum unit 33, refrigerant fluid system 34, hydrogen generating system 35, power supply system 36, fire protection alarm system 37, DCS control 38 automatically;
Described film distillator, comprise cylindrical shell and be installed on electric motor 21 and the step-down gear 18 of cylindrical shell top, step-down gear 18 is connected with through the main shaft 25 in cylindrical shell, the second scraper plate 26 for the second distributor 20 on the circumference wall reaches with downward inclination angle by the material uniformly distributing is installed on the axial wall of main shaft 25, the barrel of contiguous the second distributor 20 of cylindrical shell is provided with opening for feed 22 and light component outlet 19, the bottom end of main shaft 25 is connected with the main shaft support mechanism 29 with step-down gear 18 interlocks, the bottom of cylindrical shell is provided with heavy component collector 27 and heavy component outlet 30, the outer cover of cylindrical shell is provided with the second chuck 24 that inside is full of thermal medium, the second chuck 24 is provided with heating agent import 28 and heating agent outlet 23, material to be separated enters the second distributor 20 from opening for feed 22, through distributor, evenly material is distributed on the circumference wall, main shaft 25 is connected by bottom main shaft support mechanism 29 and step-down gear 18, with electric motor 21 systems, provide power same speed of rotation after step-down gear 18 speed changes to move in a circle, structure with oblique angle on the second distributor 20 is that the centrifugal force that material is produced with rotation according to certain angle and sendout is thrown on the circumference wall, according to the universal gravitation effect, the material of wall moves downward, and with second scraper plate 26 at downward inclination angle, material is evenly coated on the circumference wall, form filminess, material is under certain high vacuum and temperature condition, arrive the separate substance boiling point, these materials will be evaporated out phase transformation, become gas phase by liquid phase, be full of the heating medium for heating medium in the second chuck 24, from heating agent import 28, enter, from heating agent outlet 23, flow out, keep certain constant temperature, like this circumferential inner wall is heated to certain steady temperature, under certain vacuum condition, separated component will be overflowed in very thin film liquid level, the second scraper plate 26 that material is rotated on the circumference wall constantly stirs and renovation, make feed separation more thorough, because the material heated is very thin one deck, so thermo-efficiency is very high, the material be not separated is under the effect of the second scraper plate 26 centrifugal force, spin downwards and move to bottom heavy component collector 27, export 30 discharge systems by heavy component.
The preparation method of above-mentioned hydrorefining basic oil from waste internal-combustion engine oil, its special character is to comprise following technical process:
1, waste internal-combustion engine oil is delivered in sedimentation filtering system 1 and carries out the physics sedimentation, mechanical impurity is wherein removed in centrifuging, makes the content of impurities of filtering in rear waste internal-combustion engine oil be less than 0.2%;
2, waste internal-combustion engine oil after centrifuging is passed into to pretreatment system 2, then to the interior interpolation emulsion splitter of pretreatment system 2 and liquid caustic soda, carry out breakdown of emulsion except acid treatment, wherein, reach the mixing breakdown of emulsion by liquid mixer, temperature in liquid mixer is controlled at 45-80 ° of C, react 30-80 second, then vacuum hydro-extraction, waste internal-combustion engine oil water content after making to have dewatered is less than 0.1%, carry out the flash distillation processing in flashing tower, heating and temperature control in flash vaporization process is at 70-90 ° of C, vacuum pressure 9000-10000pa, some very light hydrocarbon components are separated, add solvent in waste internal-combustion engine oil after processing to flash distillation, due to pitch, colloid is not dissolved in solvent, therefore can remove by sedimentation, pass through again boiling-point difference, solvent is isolated from oil product, collection recycles,
The block polymer that the main component of described emulsion splitter is alcohols, amine, phenols and resene and oxyethane, propylene oxide, the 0.05-0.20% that the addition of emulsion splitter is the waste internal-combustion engine weight of oil;
Described liquid caustic soda is ion film caustic soda, and the weight percentage added is equal to the normal concentration of acid number in waste internal-combustion engine oil;
Described solvent is propyl alcohol, and the weight of interpolation accounts for 15% of waste internal-combustion engine weight of oil;
3, pretreated waste internal-combustion engine oil is delivered in film distillator, remove 350 ° of light component that C is following in waste internal-combustion engine oil, fill the heating medium thermal oil in chuck, it is hot face that inner cylindrical shell becomes minute surface, rotating centrifugal motion by the motor rotating mechanism, distributor is thrown to waste internal-combustion engine oil on the hot face of chuck, the scraper plate be rotated spreads to very thin film, reach the purpose that liquid level is constantly stirred to renovation, make the light component in material be gasificated into immediately gaseous state, being extracted into external condenser by vacuum unit is condensed, heavy component is not vaporized, prolonging the motion of spinning of chuck hot face downward direction, by collector, collected, film distillator chuck Heating temperature is 190～210 ° of C, the operation vacuum pressure is 200～500Pa, in the rear light component of separation, 350 ° of C cuts are lower than 1%, the segregation ratio light component accounts for 7～9% of waste internal-combustion engine oil total amount,
4, the waste internal-combustion engine oil of isolating light component is delivered in first step molecular still 6, temperature in first step molecular still 6 is controlled at 230-260 ° of C, vacuum pressure is 18-22Pa, distill 6-16 second, distill out the heat up in a steamer section of air distillation boiling range at 350 ° of C-540 ° of C, the above section of heating up in a steamer of the interior remaining 540 ° of C of first step distiller 6 is the raw material of heavy component as second stage distiller 7, temperature in second stage molecular still 7 is controlled at 260-300 ° of C, vacuum pressure is 8-12Pa, distill 6-16 second, distill out heavy fuel oil (HFO) wherein in second stage distiller 7, this heavy fuel oil (HFO) can be used as this process unit heating system boiler oil,
5, the base oil mass transport that molecular distillation is completed is to hydrogenator, fill out in hydrogenator and be placed with hydrogenation catalyst, hydrogenation catalyst accounts for 0.00175% of base oil weight of material, the ingress of hydrogenator is placed with for removing the residual heavy metal of distillation and the hydrogenation protecting agent of harmful element, the loadings of hydrogenation protecting agent is to account for base oil weight of material 18-22%, material is delivered in the first hydrogenator 8, be delivered to successively again the second hydrogenator 9 after reaction, in the 3rd hydrogenator 10, temperature in hydrogenator is controlled at 350-400 ° of C, pressure is 8.0MPa-13MPa,
Described hydrogenation catalyst is any one in Ni-W/AI2O3 type, Ni-MO/AI2O3 type, CO-MO/AI2O3 type catalyzer;
Described hydrogenation protecting agent is aluminum oxide, and the aperture of aluminum oxide is at 5-100nm;
6, the material after hydrogenation reaction is delivered in rectifying tower 5 by stripping tower 4, the effect of stripping tower is the gas and the moisture removal that are partly dissolved in hydrogenation process in base oil, it is through negative pressure heating, spouting of liquid circulated in countercurrent mode, the gas in oil product and moisture to be deviate from, isolate each other lubricant base of level by rectifying tower 5, be petrol and diesel oil component, light neutral base oil, heavy neutral base oil, separate the petrol and diesel oil component temperature and control 180-200 ° of C, vacuum pressure 9500-1000Pa; Separate light neutral base oil and control 250-270 ° of C of temperature, the remaining component neutral base oil component of attaching most importance to.
A kind of device and preparation method who utilizes waste internal-combustion engine oil refining base oil of the present invention, reasonable in design, form the commercial processes device, with low cost, waste lubricating oil is through pre-treatment and molecular distillation, isolate the refining GB II-III class base oil that obtains of base oil repeated hydrogenation, solve waste lubricating oil and can repair the GB II-III class base oil product standard that reaches, utilization ratio accounts for 83% with respect to former waste lubricating oil ratio, wherein lubricant base accounts for 75%, and after separation and purification, the component classification is: 8% heavy gas oil; (100SN+200SN+350SN) lubricant base adds up to 75%; Moisture content mechanical impurity and uncontrollable discharge thing 3%; Heavy fuel oil (HFO) 14%.Can propose highly purified base oil from waste internal-combustion engine oil, not produce any pollution in whole preparation process.Process unit comprises: the sedimentation of raw material waste lubricating oil, filtration, breakdown of emulsion, dehydration, desalination decoking, thin film distillation remove before lightweight (petrol and diesel oil) component, hight atmospheric molecular fractionation by distillation base oil, hydrogenation pre-treatment and remove that micro heavy, three sections series connection of hydrogenator are refining, rectifying tower separates each cut base oil, totally ten processing steps.
The accompanying drawing explanation
Fig. 1: a kind of apparatus structure schematic diagram that utilizes hydrorefining basic oil from waste internal-combustion engine oil of the present invention.
Fig. 2: the structural representation of molecular still;
Fig. 3: the structural representation of film distillator;
Fig. 4: the structural representation of liquid mixer.
Embodiment
Provide the specific embodiment of the invention below with reference to accompanying drawing, be used for that the present invention will be further described.
The device of a kind of hydrorefining basic oil from waste internal-combustion engine oil of the present embodiment, comprise be connected successively for filtering the sedimentation filtering system 1 of waste internal-combustion engine oil free-water and mechanical impurity, for removing, anhydrate, petroleum acid, the pretreatment system 2 of colloidal bitumen and low hydrocarbon component, for removing the film distillator 3 of 350 ° of following light component of C of boiling point, for separating of going out the 350 ° of above cuts of C of boiling point in waste internal-combustion engine oil and removing the molecular still of heavy component in waste internal-combustion engine oil, hydrogenator, mix the stripping tower 4 further separated for the hydrogenation process vapour-liquid, rectifying tower 5 for fractionation hydrofined oil different motion viscosity lubricant base.
Molecular still comprises first step molecular still 6, the second stage molecular still 7 of series connection;
Molecular still is short-distance distiller, comprise cylindrical shell 11 and be installed on the motor rotating mechanism 12 of cylindrical shell 11 tops, the agitator 14 that motor rotating mechanism 12 first distributor 15 interior with being located at cylindrical shell 11 reaches with the first scraper plate 17 is connected, the inside of agitator 14 is provided with condenser, condenser is connected with the first collector 16, cylindrical shell 11 outer cover are provided with in the first chuck 13, the first chucks 13 and are filled with heat-conducting medium; During work, by the 12 rotating centrifugal motions of motor rotating mechanism, the first distributor 15 is thrown to waste internal-combustion engine oil on the hot face of interior chuck, and the first scraper plate 17 knifing, reach the liquid level effect of constantly updating, be convenient to the evaporation of material component thermally equivalent, pass into mobile coolant media in the interior stainless steel shell-and tube condenser of agitator 14, for the oil vapour condensation rapidly evaporation, become liquid and collect, heavy component is not evaporated, and by molecular still bottom the first collector 16, is collected;
Hydrogenator comprises the first hydrogenator 8, the second hydrogenator 9, the 3rd hydrogenator 10 be in series;
The device of waste internal-combustion engine oil refining base oil also comprises that heating system 31, circulating water system 32, water-circulation type vacuum and high vacuum unit 33, refrigerant fluid system 34, hydrogen generating system 35, power supply system 36, fire protection alarm system 37, DCS control 38 automatically;
Film distillator, comprise cylindrical shell and be installed on electric motor 21 and the step-down gear 18 of cylindrical shell top, step-down gear 18 is connected with through the main shaft 25 in cylindrical shell, the second scraper plate 26 for the second distributor 20 on the circumference wall reaches with downward inclination angle by the material uniformly distributing is installed on the axial wall of main shaft 25, the barrel of contiguous the second distributor 20 of cylindrical shell is provided with opening for feed 22 and light component outlet 19, the bottom end of main shaft 25 is connected with the main shaft support mechanism 15 with step-down gear 18 interlocks, the bottom of cylindrical shell is provided with heavy component collector 27 and heavy component outlet 30, the outer cover of cylindrical shell is provided with the second chuck 24 that inside is full of thermal medium, the second chuck 24 is provided with heating agent import 28 and heating agent outlet 23, material to be separated enters the second distributor 20 from opening for feed 7, through distributor, evenly material is distributed on the circumference wall, main shaft 25 is connected by bottom main shaft support mechanism 29 and step-down gear 18, with electric motor 21 systems, provide power same speed of rotation after step-down gear 1 speed change to move in a circle, structure with oblique angle on the second distributor 20 is that the centrifugal force that material is produced with rotation according to certain angle and sendout is thrown on the circumference wall, according to the universal gravitation effect, the material of wall moves downward, and with second scraper plate 26 at downward inclination angle, material is evenly coated on the circumference wall, form filminess, material is under certain high vacuum and temperature condition, arrive the separate substance boiling point, these materials will be evaporated out phase transformation, become gas phase by liquid phase, be full of the heating medium for heating medium in the second chuck 24, from heating agent import 28, enter, from heating agent outlet 23, flow out, keep certain constant temperature, like this circumferential inner wall is heated to certain steady temperature, under certain vacuum condition, separated component will be overflowed in very thin film liquid level, the second scraper plate 26 that material is rotated on the circumference wall constantly stirs and renovation, make feed separation more thorough, because the material heated is very thin one deck, so thermo-efficiency is very high, the material be not separated is under the effect of the second scraper plate 26 centrifugal force, spin downwards and move to bottom heavy component collector 27, export 30 discharge systems by heavy component.
Adopt the preparation method of above-mentioned waste internal-combustion engine oil refining base oil device, be applicable to the waste lubricant of internal combustion engine, the gear wet goods waste mineral oil that reclaim.Processing technology routine:
The raw material waste lubricating oil is through pre-treatment; Natural subsidence, remove the petroleum acid in waste oil, filters mechanical impurity wherein, adds emulsion splitter to impel and remove oily water separation, through flashing tower, removes the moisture in waste oil; Add solvent to make colloid, the salinity precipitate and separate in waste lubricating oil, the solvent Distillation recovery recycles.
Utilize thin-film evaporator to isolate 350 ° of following petrol and diesel oil components of C; again heavy component is isolated in molecular still to base oil and heavy component; the gained lubricant base meets the hydrogenation condition for import; fractionate out and obtain each other base oil product of level through rectifying again after hydrogenation reaction; the pre-treatment of process front end before hydrogenation; be that at first base oil passes through the hydrogenation protecting agent, absorption trace metal wherein, with the work-ing life of protection hydrogenation catalyst.
After the hydrogenator of three sections series connection, prerequisite, the irrational component in base oil is removed, then goes out each other lubricant base of level through rectifying separation.
Specifically comprise following technical process:
1, waste internal-combustion engine oil is delivered in sedimentation filtering system 1 and carries out the physics sedimentation, mechanical impurity is wherein removed in centrifuging, makes the content of impurities of filtering rear waste internal-combustion engine oil be less than 0.2%;
2, the waste internal-combustion engine oil after centrifuging is passed into to pretreatment system 2, carry out breakdown of emulsion except acid treatment.Perhaps can contain certain moisture in waste internal-combustion engine oil, a part is free water, another part is emulsified water, emulsified water must add emulsion splitter can become free water, waste internal-combustion engine oil is because in use oxidation becomes acidity, need to add organic bases or mineral alkali neutralization, the block polymer that the emulsion splitter composition is alcohols, amine, phenols, resene and oxyethane, propylene oxide, addition is 0.1% of waste internal-combustion engine oil mass, reach the mixing breakdown of emulsion by liquid mixer, technological temperature is 45～80 ° of C.Then vacuum hydro-extraction, the waste internal-combustion engine oil water content after making to have dewatered is less than 0.1%.
Pre-treatment be by waste internal-combustion engine oil moisture, impurity, asphalt colloid remove, thereby reach thin membrane distillation condition for import, light component separates thoroughly can be not unfavorable to subsequent processing, waste internal-combustion engine oil contains a certain amount of pitch, colloid and heavy metal, these compositions can be blocked the catalyzer micropore in hydrogenation process, heavy metal can cause poisoning of catalyst, catalyzer is progressively lost activity, therefore must remove, just must remove colloid, pitch before advancing film distillator, specifically adopt the dissolution with solvents method; Pitch, colloid are not dissolved in solvent, through sedimentation, remove, and solvent is different from waste internal-combustion engine oil boiling point, by boiling-point difference, separated from solvent is gone out in oil product to collect and recycle.
3, pretreated waste internal-combustion engine oil is delivered in film distillator, removes the light component in waste internal-combustion engine oil; Film distillator is comprised of cylindrical shell and the motor rotating mechanism of jacketed, in chuck, is that thermal oil is heating medium, and it is hot face that inner cylindrical shell becomes minute surface; Belt scraping plate agitator and distributor that high-seal is arranged, rotating centrifugal motion by motor, distributor is thrown to waste internal-combustion engine oil on the hot face of interior chuck, what be rotated spreads to very thin film with the angle scraper plate, scraper plate also plays the purpose that rete is constantly stirred and renovates, make the light component in material flash to immediately gaseous state from mixed solution, being extracted into external condenser by vacuum is condensed, heavy component is not vaporized, in prolonging, the motion of spinning of chuck hot face downward direction, collected by collector.Film distillator chuck Heating temperature is 190～210 ° of C, and the operation vacuum pressure is 200～500Pa, and after separating, in heavy component, 350 ° of C cuts are lower than 1%, and the segregation ratio light component accounts for 7～9% of waste internal-combustion engine oil total amount.
4, the heavy component stock oil that will isolate the light component remainder is delivered in first step molecular still 6, distill out wherein relatively light base oil component, in first step distiller, remaining heavy component is as the raw material of second stage distiller 7, distill out wherein slightly heavy heavy fuel oil (HFO), this heavy fuel oil (HFO) can be used as this process unit heating system boiler oil; First step molecular still service temperature is 245 ° of C, vacuum pressure 20Pa, and base oil (light component) ratio accounts for 60% of inlet amount; 280 ° of C of second stage molecular still service temperature, vacuum pressure is 10Pa, the base oil ratio accounts for inlet amount 60%.
5, base oil mass transport molecular distillation completed is to fixed bed hydrogenation reactor, three layers of fixed bed are arranged in hydrogenator, fill out respectively and put hydrogenation special-purpose catalyzer, reactor top is placed the hydrogenation protecting agent, hydrogenation catalyst loses activity and mainly contains three reasons: the one, and blockage of the micro orifice, the 2nd, metal poisoning, the 3rd, sedimentation of coke; Distillation residual heavy metal and harmful element are mainly removed in the hydrogenation protecting agent; loadings is to account for total amount 1/5; material must first pass through the hydrogenation protecting agent before contacting with hydrogenation catalyst, after the removal objectionable impurities, to hydrogenation catalyst, make a return journey denitrogenate, the compounds such as sulphur, oxygen.Material is delivered in the first hydrogenator 8, be delivered to successively again after reaction in the second hydrogenator 9, the 3rd hydrogenator 10; The lubricant base of China is II class and III class oil from external import volume maximum at present, consider that hydrorefined base oil can reach national II class, III class oil standard, select three grades of hydrogenators, hydrogenation catalyst is Ni-W/AI2O3 type, Ni-MO/AI2O3 type, CO-MO/AI2O3 type catalyzer, 350～400 ° of C of temperature, pressure is 8.0MPa～13MPa.
6, the material after hydrogenation reaction is delivered in rectifying tower 5 by stripping tower 4, by rectifying tower 5, isolates each other lubricant base of level, i.e. petrol and diesel oil component, light neutral base oil, heavy neutral base oil.The rectifying tower operation, by the batch quantity circulation, separates the petrol and diesel oil component temperature and controls 190 ° of C, vacuum pressure 9700Pa; Separate light neutral base oil and control 260 ° of C of temperature, the remaining component neutral base oil component of attaching most importance to.
Waste internal-combustion engine oil raw material index is as follows: table 1. waste lubricant of internal combustion engine character
After the present embodiment step 3 molecular distillation, in the regenerated internal combustion (IC) engine lubricating oil, the ingredient index is as shown in the table: table 2: regenerating waste lubricant of internal combustion engine material property matter
| Analysis project | Data |
| Sulphur/μ gg -1 | 1075 |
| Nitrogen/μ gg -1 | 0 |
| C/H/% | 81.40/13.55 |
| Condensation point/℃ | —20 |
| Viscosity (100 ℃)/mm 2·s -1 | 4.477 |
| Viscosity (40 ℃)/mm 2·s -1 | 21.94 |
| Carbon residue, % | 0.03 |
| Bromine valency/g-Br/100g | 2.56 |
| Acid number/mgKOH/g | 0.26 |
| Flash-point/℃ | 206.0 |
| Mass spectrum composition/m% | |
| Paraffinic hydrocarbons | 45.8 |
| Naphthenic hydrocarbon | 48.0 |
| One ring/bis-ring/tri-ring/Fourth Rings/five rings/six rings | 16.3/13.6/7.6/6.7/3.7/0.1 |
| Aromatic hydrocarbons | 6.2 |
| Monocycle/dicyclo/tri-ring/Fourth Rings/five rings | 3.4/1.7/0.4/0.1/0.2 |
| Thiophene/do not identify aromatic hydrocarbons | 0.3/0.3 |
| Four components/% | |
| Saturated minute | 96.76 |
| Fragrance minute | 0.46 |
| Colloid | 2.77 |
| Bituminous matter | 0.10 |
| Heavy metal/μ g.g -1 | |
| Fe /K/Pb/ Mn | 0.71/0.08/0.01/0.03 |
| Na/Ni /Zn/Mg | 0.18/0.02/0.16/0.14 |
| Ca/Cu/Mo | 4.36/0.01/0.03 |
Through allowing machine oil reach II-III class base oil index as following table in the present embodiment step 4 hydrofining postchannel process regenerated:
Table 3: allow machine oil reach II-III class base oil index in hydrofining postchannel process regenerated
| Analysis project | Data |
| Sulphur/μ gg -1 | 0 |
| Nitrogen/μ gg -1 | 0 |
| C/H/% | 81.40/13.55 |
| Condensation point/℃ | —20 |
| Viscosity (100 ℃)/mm 2·s -1 | 4.477 |
| Viscosity (40 ℃)/mm 2·s -1 | 21.94 |
| Carbon residue, % | 0.01 |
| Bromine valency/g-Br/100g | 0 |
| Acid number/mgKOH/g | 0.01 |
| Flash-point/℃ | 206.0 |
| Mass spectrum composition/m% | |
| Paraffinic hydrocarbons | 45.8 |
| Naphthenic hydrocarbon | Be greater than 48.0 |
| One ring/bis-ring/tri-ring/Fourth Rings/five rings/six rings | 16.3/13.6/7.6/6.7/3.7/0.1 |
| Aromatic hydrocarbons | 0 |
| Monocycle/dicyclo/tri-ring/Fourth Rings/five rings | 3.4/1.7/0.4/0.1/0.2 |
| Thiophene/do not identify aromatic hydrocarbons | 0 |
| Four components/% | |
| Saturated minute | Be greater than 96.76 |
| Fragrance minute | 0 |
| Colloid | 0 |
| Bituminous matter | 0.01 |
| Heavy metal/μ g.g -1 | |
| Fe /K/Pb/ Mn | 0 |
| Na/Ni /Zn/Mg | 0 |
| Ca/Cu/Mo | 0 |
Molecular distillation technique is as a kind of high-new isolation technique of synchronizeing with the world, it is to utilize free path difference different between molecule to realize separating, this technology is applied to the earliest pharmacy and chemical industry is purified, for separating of waste internal-combustion engine oil base oil, be exactly molecular distillation technique in fact according to lubricated oil properties, avoid cracking coking in pyroprocess, because thin film distillation, the whole sepn process of molecular distillation is that the feed separation process is all physical changes, can not affect the molecular structure of lubricating oil, adopt high vacuum, allow exactly mineral oil seethe with excitement and become the gaseous state phase transformation at the temperature lower than boiling point.The gaseous component that molecular still has built-in condenser to make like this to separate evaporation is liquefy and realize disposable separation immediately, and is unresisted separation, well below the temperature condition that can cause destroying its molecular structure; Film distillator, the inner high-efficiency rotating scraper plate of molecular still can not produce the material of film forming the heating dead angle on cylindrical wall, form film constantly renovation in inside, thereby reach the thermally equivalent purpose, heat utilization rate is very high, can reach high efficiency separation again can energy saving.Its separation principle figure is shown in as shown in Figure 2.
The present invention just can reach into the molecular distillation condition for import by pre-treatment; pass through again the front hydrogenation protecting agent effect of hydrogenation; make oil product reach the condition for import of hydrogenator, whole invention is the undesirable components in waste internal-combustion engine oil to be carried out to innoxious separation step by step deviate from process.
Waste internal-combustion engine oil is understood some additives decompose after molecular distillation, and some sulfide of some releases and nitride, muriate can make oil product peculiar smell occur;
Adopting hydrogen addition technology is to improve product quality, realizes this class waste oil processing one of effective means of purifying.
(1) there are various oxidation productss in waste oil, mainly carboxylic acid, ester, aldehyde, ketone, alcohols, phenols, peroxide, oxygenatedchemicals is the easiest hydrogenation, and generally very fast response generates corresponding hydrocarbon and water, also be accompanied by the reactions such as de-alkyl isomerization, condensation open loop simultaneously;
(2) reaction rapidly under hydroconversion condition of the sulfocompound in waste oil, generate corresponding hydrocarbon and hydrogen sulfide;
(3) halogenide in waste oil is mainly chlorocarbon, generates hydrogenchloride and corresponding hydrocarbon during the chlorocarbon hydrogenation;
(4) the by product product produced in the stage at shortening is as muriate and sulfide, be admitted to alkali one water wash system together with unreacted hydrogen, carry out neutralization reaction, muriate and sulfide are deviate from, remaining hydrogen has obtained purification, returns in the operation of front.The lubricating oil produced in reaction and light component are admitted to rectifying tower and carry out fractionation, obtain light neutral base oil and heavy neutral base oil.
Customized catalyzer be take aluminum oxide as carrier, many beds hydrogenator, to improve the different demand activity and selectivities such as hydrogenating desulfurization, denitrogenation, oxide removal, make the surface-area of catalyzer and the needs that pore distribution adapts to different material oil better, the running period of extending catalyst and work-ing life, reduce the cost of producing catalyzer metal component used, the Optimization Technology process.
Process unit of the present invention is realized environmental protection:
(1) waste water: a small amount of oily(waste)water that waste internal-combustion engine oil removes goes this process unit to burn together with fuel with heat boiler, and punching ground water also goes to burn when boiler oil after oil trap.
(2) waste gas: in the uncontrollable discharge exhaust gas centralized that in process unit, each vacuum unit, tower are discharged, be extracted in boiler and burn.
(3) machine is assorted: the waste internal-combustion engine oil filter is assorted, goes boiler to burn, whole disposal process environmental protection.
Claims (9)
1. the device of a hydrorefining basic oil from waste internal-combustion engine oil, it is characterized in that comprising be connected successively for filtering the sedimentation filtering system (1) of waste internal-combustion engine oil free-water and mechanical impurity, for removing, anhydrate, petroleum acid, the pretreatment system (2) of colloidal bitumen and low hydrocarbon component, for removing the film distillator (3) of 350 ° of following light component of C of boiling point, for separating of going out the 350 ° of above cuts of C of boiling point in waste internal-combustion engine oil and removing the molecular still of heavy component in waste internal-combustion engine oil, hydrogenator, mix the stripping tower (4) further separated for the hydrogenation process vapour-liquid, rectifying tower (5) for fractionation hydrofined oil different motion viscosity lubricant base,
Described pretreatment system (2) comprises the liquid mixer that makes emulsified water breakdown of emulsion, petroleum acid neutralization for waste oil and emulsion splitter, liquid caustic soda are fully mixed, liquid mixer inside is the spiral net-shaped structure, and liquid mixer is provided with the butterfly supercentrifuge (39) of free water content for filtering waste internal-combustion engine oil and mechanical impurity and for removing the flashing tower (40) of a small amount of moisture that waste internal-combustion engine oil contains.
2. according to the device of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 1, it is characterized in that described molecular still comprises first step molecular still (6), the second stage molecular still (7) of series connection.
3. according to the device of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 1, it is characterized in that described molecular still is short-distance distiller, comprise cylindrical shell (11) and be installed on the motor rotating mechanism (12) of cylindrical shell (11) top, the agitator (14) that motor rotating mechanism (12) first distributor (15) interior with being located at cylindrical shell (11) reaches with the first scraper plate (17) is connected, the inside of agitator (14) is provided with condenser, condenser is connected with the first collector (16), cylindrical shell (11) outer cover is provided with the first chuck (13), the first chuck is filled with heat-conducting medium in (13).
4. according to the device of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 1, it is characterized in that described hydrogenator comprises the first hydrogenator (8), the second hydrogenator (9), the 3rd hydrogenator (10) be in series.
5. according to the device of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 1, it is characterized in that the device of described waste internal-combustion engine oil refining base oil also comprises that heating system (31), circulating water system (32), water-circulation type vacuum and high vacuum unit (33), refrigerant fluid system (34), hydrogen generating system (35), power supply system (36), fire protection alarm system (37), DCS control (38) automatically.
6. according to the device of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 1, it is characterized in that described film distillator
,comprise cylindrical shell and be installed on electric motor (21) and the step-down gear (18) of cylindrical shell top, step-down gear (18) is connected with through the main shaft (25) in cylindrical shell, on the axial wall of main shaft (25), be equipped with for by the material uniformly distributing, the second distributor (20) on the circumference wall reaches the second scraper plate (26) with downward inclination angle, the barrel of contiguous the second distributor of cylindrical shell (20) is provided with opening for feed (22) and light component outlet (19), the bottom end of main shaft (25) is connected with the main shaft support mechanism (29) with step-down gear (18) interlock, the bottom of cylindrical shell is provided with heavy component collector (27) and heavy component outlet (30), the outer cover of cylindrical shell is provided with the second chuck (24) that inside is full of thermal medium, the second chuck (24) is provided with heating agent import (28) and heating agent outlet (23).
7. the preparation method of a hydrorefining basic oil from waste internal-combustion engine oil is characterized in that comprising following technical process:
1), waste internal-combustion engine oil is delivered in sedimentation filtering system (1) and carries out the physics sedimentation, mechanical impurity is wherein removed in centrifuging, makes the content of impurities of filtering in rear waste internal-combustion engine oil be less than 0.2%;
2), waste internal-combustion engine oil after centrifuging is passed into to pretreatment system (2), then add emulsion splitter and liquid caustic soda in pretreatment system (2), carry out breakdown of emulsion except acid treatment, wherein, reach the mixing breakdown of emulsion by liquid mixer, temperature in liquid mixer is controlled at 45-80 ℃, react 30-80 second, then vacuum hydro-extraction, waste internal-combustion engine oil water content after making to have dewatered is less than 0.1%, carry out the flash distillation processing in flashing tower, heating and temperature control in flash vaporization process is at 70-90 ℃, vacuum pressure 9000-10000Pa, some very light hydrocarbon components are separated, add solvent in waste internal-combustion engine oil after processing to flash distillation, due to pitch, colloid is not dissolved in solvent, therefore can remove by sedimentation, pass through again boiling-point difference, solvent is isolated from oil product, collection recycles,
3), pretreated waste internal-combustion engine oil is delivered in film distillator, remove the light component below 350 ℃ in waste internal-combustion engine oil, fill the heating medium thermal oil in chuck, it is hot face that inner cylindrical shell becomes minute surface, rotating centrifugal motion by the motor rotating mechanism, distributor is thrown to waste internal-combustion engine oil on the hot face of chuck, the scraper plate be rotated spreads to very thin film, reach the purpose that liquid level is constantly stirred to renovation, make the light component in material be gasificated into immediately gaseous state, being extracted into external condenser by vacuum unit is condensed, heavy component is not vaporized, spin and move along chuck hot face downward direction, by collector, collected, film distillator chuck Heating temperature is 190～210 ℃, the operation vacuum pressure is 200～500Pa, in the rear light component of separation, 350 ℃ of cuts are lower than 1%, the segregation ratio light component accounts for 7～9% of waste internal-combustion engine oil total amount,
4), the waste internal-combustion engine oil of isolating light component is delivered in first step molecular still (6), temperature in first step molecular still (6) is controlled at 230-260 ℃, vacuum pressure is 18-22Pa, distill 6-16 second, distill out the air distillation boiling range the section of heating up in a steamer of 350 ℃-540 ℃, in first step molecular still (6), the remaining section of heating up in a steamer more than 540 ℃ is the raw material of heavy component as second stage molecular still (7), temperature in second stage molecular still (7) is controlled at 260-300 ℃, vacuum pressure is 8-12Pa, distill 6-16 second, distill out heavy fuel oil (HFO) wherein in second stage molecular still (7), this heavy fuel oil (HFO) is as this process unit heating system boiler oil,
5), the base oil mass transport that molecular distillation is completed is to hydrogenator, fill out in hydrogenator and be placed with hydrogenation catalyst, hydrogenation catalyst accounts for 0.00175% of base oil weight of material, the ingress of hydrogenator is placed with for removing the residual heavy metal of distillation and the hydrogenation protecting agent of harmful element, the loadings of hydrogenation protecting agent is to account for base oil weight of material 18-22%, material is delivered in the first hydrogenator (8), be delivered to successively again the second hydrogenator (9) after reaction, in the 3rd hydrogenator (10), temperature in hydrogenator (10) is controlled at 350-400 ℃, pressure is 8.0MPa-13MPa,
6), the material after hydrogenation reaction is delivered in rectifying tower (5) by stripping tower 4, isolate each other lubricant base of level by rectifying tower (5), be petrol and diesel oil component, light neutral base oil, heavy neutral base oil, separate the petrol and diesel oil component temperature and control 180-200 ℃, vacuum pressure 9500-1000Pa; Separate light neutral base oil and control temperature 250-270 ℃, the remaining component neutral base oil component of attaching most importance to.
8. according to the preparation method of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 7, it is characterized in that
2) in
The block polymer that the main component of described emulsion splitter is alcohols, amine, phenols and resene and oxyethane, propylene oxide, the 0.05-0.20% that the addition of emulsion splitter is the waste internal-combustion engine weight of oil;
Described liquid caustic soda is ion film caustic soda, and the weight percentage added is equal to the normal concentration of acid number in waste internal-combustion engine oil.
9. according to the preparation method of a kind of hydrorefining basic oil from waste internal-combustion engine oil claimed in claim 7, it is characterized in that
5) agent of hydrogenation protecting described in is aluminum oxide, and the aperture of aluminum oxide is at 5-100nm.
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| CN103351939B (en) * | 2013-06-28 | 2015-01-21 | 姜皓 | Refine and regeneration method of waste lubricant oil and regeneration device thereof |
| CN104611058B (en) * | 2015-02-05 | 2016-07-13 | 武汉科林精细化工有限公司 | A kind of hydrofining technology of waste lubricating oil |
| CN104830514B (en) * | 2015-04-21 | 2018-04-17 | 于胜宾 | A kind of renovation process of waste lubricating oil |
| CN106350112B (en) * | 2015-07-14 | 2017-12-15 | 新疆聚力环保科技有限公司 | A kind of waste mineral oil pretreatment-the method for hydrogenation reclaimed lubricating oil base oil |
| CN105524702B (en) * | 2015-12-22 | 2018-04-06 | 西安石油大学 | Waste lubricating oil environment protection regeneration method |
| CN107574011B (en) * | 2017-09-13 | 2021-02-05 | 宁波中循环保科技有限公司 | Regeneration treatment method for complexing, membrane separation, hydrogenation and fractionation of waste lubricating oil |
| CN108822954A (en) * | 2018-07-26 | 2018-11-16 | 广东新生环保科技股份有限公司 | A kind of abandoned mine oil recovery system |
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| CN113430045B (en) * | 2021-08-27 | 2021-10-29 | 东营国安化工有限公司 | Separation device and method for removing impurities in waste lubricating oil |
| CN115612548A (en) * | 2022-10-31 | 2023-01-17 | 鲁西化工集团股份有限公司煤化工一分公司 | Waste oil refining method |
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